Oxidant detergent containing stable bleach activator granules

ABSTRACT

The present invention provides stable bleach activator granules comprising: 
     a) a peroxygen bleach activator having the structure: ##STR1##  wherein R is C 1-20  branched or straight chain alkyl, alkoxylated alkyl, cycloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R&#39; and R&#34; are independently H, C 1-4  alkyl, aryl; and L is a leaving group; 
     b) a pliable binding material selected from materials having a melting completion temperature of greater than about 40° C.; and, optionally, 
     c) a filler material. 
     These bleach activator granules are combined with a detergent base which contains an oxidant bleach to provide an activated oxidant detergent composition.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to stable bleach activator granules,specifically, granules which contain activators with the structure:##STR2##

wherein R is C₁₋₂₀ branched or straight chain alkyl, alkoxylated alkyl,cycloalkyl, substituted aryl, alkenyl, aryl, alkylaryl; R' and R" areindependently H, C₁₋₄ alkyl, aryl; and L is a leaving group.

These activator granules are combined with a detergent base whichcomprises

builders; and

a surfactant selected from the group consisting of anionic, nonionic,cationic, amphoteric, zwitterionic surfactants, and mixtures thereof;and

a bleach-effective amount of a source of hydrogen peroxide to act withthe activator granules.

2. Brief Description of the Prior Art

Bleach activators have been widely described in the literature. Forexample, Boldingh et al., U.K. 1,147,871, describes bleaching anddetergent comPositions containing an inorganic persalt and acyloxyalkylor acyl benzene sulfonates. It is claimed that such esters provideimproved bleaching temperatures below 70° C. when compared tocompositions using the persalt alone.

These activators are represented by the formula: ##STR3## whereinX=branched or straight chain alkyl or acyl radical containing 6-17carbon atoms; R=H or alkyl radical having 1-7 carbon atoms; and M= analkali metal, or ammonium radical.

Chung et al., U.S. Pat. No. 4,412,934, discloses bleaching compositionscontaining a peroxygen bleaching compound and a bleach activator of thegeneral formula ##STR4## wherein R is an alkyl group containing fromabout 5 to about 18 carbon atoms; L is a leaving group, the conjugateacid of which has a pK_(a) in the range of about 6 to about 13. Chung etal. focuses on alkanoyloxy benzene sulfonates, which have beenpreviously disclosed in G. B. 864,798, Hampson et al.

Thompson et al, U.S. Pat. No. 4,483,778, discloses bleach activators ofthe structure ##STR5## wherein R is C₄₋₁₄ alkyl, R¹ is H or C₁₋₃ alkyl,X is --Cl, --OCH₃, or --OCH₂ CH₃, and L is a leaving group whoseconjugate acid has a pK_(a) of 4-30. The apparently crowded alpha carbonin the Thompson et al. compound may present hindered perhydrolyticreactivity. Hardy et al., U.S. Pat. No. 4,681,592, discloses the use ofa bleach activator compound of the formula [RX]_(m) AL, wherein R ishydrocarbyl, C₆₋₂₀ alkyl substituted aryl, or alkoxylated hydrocarbyl; Xis O, SO₂, N(R¹)₂, (R¹)P→O or (R¹)N→O, wherein for m=1, A includes##STR6## oxybenzene sulfonate.

Burns et al., U.S. Pat. No. 4,634,551, discloses the use of amide estersof the formula ##STR7## wherein R¹ and R² are alkyl(ene) aryl(ene) oralkylaryl(ene) with 1-14 carbon atoms and R⁵ is H, an alkyl, aryl, oralkylaryl group with 1-10 carbon atoms.

Nakagawa et al., U.S. Pat. No. 3,960,743, disclose polymeric activatorshaving the general structure ##STR8## in which R is purported to beC₁₋₁₆ carbon atoms, a halo-- or hydroxyl-substituted C₁₋₁₆ alkyl or asubstituted aryl group, B is hydrogen or a C₁₋₃ alkyl group, M ishydrogen, C₁₋₄ alkyl or alkali metal, wherein n is an integer of atleast one when M is an alkyl group or n is an integer of least two whenM is hydrogen or alkali metal. The polymeric activators of Nakagawa etal., however, suffer from a fatal defect. They do not disclose, teach orsuggest perhydrolysis leaving groups.

Schirmann et al., U.S. Pat. No. 4,221,675, substituted acyloxyN-acetamides of the structure ##STR9##

The activators of the present invention do not contain a nitrogenheteroatom as does the activator of Schirmann et al. Moreover, inSchirmann et al., the group in question, an amide, does not bind to theacyl portion of the compound via an oxygen bond. Schirmann et al. do notteach or suggest what peracid is generated or where Perhydrolysisoccurs. APPlicants have demonstrated that the alpha acyloxy,N-acetylacetamide compounds disclosed in Schirmann et al. provideminimal perhydrolysis at site of the amide bond, if at all, and thus donot effectively generate the desired peracid, peralkanoyloxyacetic acid.Thus, Schirmann et al. also do not have an effective leaving group.

Various references have taught how to formulate bleach activatorgranules using activators of the prior art. For example, Corey et al.,U.S. Pat. No. 3,661,789, Green et al., U.S. 4,009,113, Wevers, U.S. Pat.No. 4,087,369, Saran, U.S. Pat. No. 4,372,868, Gray et al., U.S. Pat.No. 4,399,049, Gray, U.S. Pat. No. 4,444,674, Thompson et al., U.S.4,483,778, Murphy et al., U.S. Pat. No. 4,486,327, Thompson et al., U.S.4,539,130, Chung et al., E. P. 106,634, Parfomak, U.K. 2,178,075 andDivo, U.S. Pat. No. 4,681,695, all discuss ways of combining a peroxygenbleach activator with some binding or enrobing material.

However, none of the foregoing references teaches, discloses or suggestsbleach activator granules with the structure ##STR10## wherein R isC₁₋₂₀ branched or straight chain alkyl, alkoxylated alkyl, cycloalkyl,alkenyl, aryl, substituted aryl, alkylaryl; R' and R" are independentlyH, C₁₋₄ alkyl, aryl; and L is a leaving group.

Moreover, none of the art discloses, teaches or suggests that activatorsof the above structure can be incorporated in stabilized granules withimproved perhydrolysis efficiency over the powdered activator alone.Additionally, none of the art discloses, teaches or suggests thatactivators of this type can be granulated with binding materials whichhave a melting completion temperature of at least about 40° C, saidbinding materials being in relatively small quantity with respect to theactivator. Also, none of the art discloses, teaches or suggests thatwhen these activator granules are incorporated into a detergent base,some detergent surfactants are preferred over others, and that certainstabilizing materials are especially preferred.

SUMMARY OF THE INVENTION AND OBJECTS

The invention provides, in one embodiment, stable bleach activatorgranules comprising:

(a) a Peroxygen bleach activator having the structure: ##STR11## whereinR is C₁₋₂₀ branched or straight chain alkyl, alkoxylated alkyl,cycloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R' and R" areindependently H, C₁₋₄ alkyl, aryl; and L is a leaving group;

(b) a pliable binding material selected from materials having a meltingcompletion temperature of greater than about 40° C.; and, optionally,

(c) a filler material.

In another embodiment, the invention provides stable bleach activatorgranules comprising:

(a) a peroxygen bleach activator having the structure: ##STR12## whereinR is C₁₋₂₀ branched or straight alkyl, alkoxylated alkyl, cycloalkyl,alkenyl, aryl, substituted aryl, alkylaryl; R' and R" are independentlyH, C₁₋₄ alkyl, aryl; and L is a leaving group;

(b) an inorganic or organic binding material;

wherein said granules are approximately cylindrical or spherical, andhave a diameter of about 25 to 2,000 microns, dissolve, in water, withinabout 10 minutes at 21° C., and have a pH of about 5 to 8 in water.

In still another embodiment, the invention provides an activated oxidantdetergent comprising:

(a) bleach activator granules comprising:

(i) a peroxygen bleach activator having the structure: ##STR13## whereinR is C₁₋₂₀ branched or straight chain alkyl, alkoxylated alkyl,cycloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R' and R" areindependently H, C₁₋₄ alkyl, aryl; and L is a leaving group;

(ii) a pliable binding material selected from materials having a meltingcompletion temperature of greater than about 40° C.; and, optionally,

(iii) a filler material;

(b) a detergent base which comprises:

(i) builders;

(ii) fillers;

(iii) a surfactant selected from the group consisting of anionic,nonionic, cationic, amphoteric, zwitterionic surfactants, and mixturesthereof; and

(c) a bleach-effective amount of a source of hydrogen peroxide, whichacts in combination with the activator granules of (a).

It is therefore an object of this invention to provide stable bleachingactivator granules as hereinbefore described.

It is another object of this invention to enhance the performance ofbleaching activator granules as hereinbefore described over that of thepowdered activator.

It is still another object of this invention to provide bleach activatorgranules which are easily and efficiently processible.

It is yet another object of this invention to provide bleach activatorgranules which have as a majority of their content, the bleach activatorcompound.

It is a further object of this invention to provide an oxidant detergentcomposition which includes the stable bleach activator granules.

It is a still further object of this invention to improve the launderingPerformance of said oxidant detergent composition by careful selectionof surfactants.

It is also an object of this invention to enhance the performance ofsaid oxidant detergent by careful selection of stabilizing additives.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a flow chart describing the manufacture of the bleachactivator granules.

The present invention Provides stable bleach activator granulescomprising:

(a) a peroxygen bleach activator having the structure: ##STR14## whereinR is C₁₋₂₀ branched or straight chain alkyl, alkoxylated alkyl, ,cycloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R' and R" areindependently H, C₁₋₄ alkyl, aryl; and L is a leaving group;

(b) a pliable binding material selected from materials having a meltingcompletion temperature of greater than about 40° C.; and, optionally,

(c) a filler material.

The parent application, Ser. No. 06/928,070, filed Nov. 6, 1986,disclosed and claimed the activators which the Applicants process intothe present inventive granules. The advantages of said activators areamply discussed in the specification of said application. WhileApplicants discuss some of the advantages of said activators in thisapplication, for the sake of brevity, Applicants have incorporated Ser.No. 06/928,070 by reference thereto as if fully set forth herein, andwill rely on its discussion therein. Additionally of interest is therelated application of Richard R. Rowland, Ser. No. 07/167,544, filedMar. 14, 1988, entitled "METHOD FOR SYNTHESIZING ACYLOXYCARBOXYLICACIDS," which discloses methods of acylating the hydroxycarboxylic acidswhich are predecessors to the activators of this invention. Saidapplication is incorporated herein by reference.

Of particular interest from application Ser. No. 06/928,070 is aparticularly preferred activator, namely, ##STR15##

These types of activators are referred to as alkanoylglycolate oralkanoyloxyacetic acid esters, since their base carbonyl group is##STR16##

These types of activators provide numerous benefits over the prior arttype activators. The Nakagawa et al. type polymeric activators do notteach, disclose or suggest a leaving group and if their monomer is usedas an activator, little or no perhydrolysis occurs. The Schirmann et al.type activators similarly have little or no perhydrolysis.

In the following discussion, certain definitions are utilized:

Peracid precursor is equivalent to bleach activator. Both termsgenerally relate herein to reactive esters which have a leaving groupsubstituent, which during perhydrolysis, actually cleaves off the acylportion of the ester.

Perhydrolysis is the reaction which occurs when a peracid precursor oractivator is combined in a reaction medium (aqueous medium) with aneffective amount of a source of hydrogen peroxide.

The leaving group, L, is basically a substituent which is attached viaan oxygen bond to the acyl portion of the ester and which can bereplaced by a Perhydroxide anion (OOH ) during perhydrolysis.

The basic reaction is: ##STR17##

Although further discussion below will elaborate on the uniqueadvantages of the preferred embodiment, ##STR18## also referred to as aglycolate ester or as an acylglycolate ester, at present, theconstituent portions of the ester, i.e., the acyl group and the leavinggroups are herein defined.

R is defined as being C₁₋₂₀ linear or branched alkyl, alkoxylated alkyl,cycloalkyl, alkenyl, aryl, substituted aryl or alkylaryl.

It is preferred that R is C₁₋₂₀ alkyl or alkoxylated alkyl. Morepreferably, R is C₁₋₁₀, and mixtures thereof. R can also bemono-unsaturated or polyunsaturated. If alkoxylated, ethoxy (EO)--(--OCH₂ CH₂) and propoxy (PO) --(--OCH₂ CH₂ CH₂), ##STR19## groups arepreferred, and can be present, per mole of ester, from 1-30 EO or POgroups, and mixtures thereof.

It is especially preferred for R to be from 4 to 17, most preferably 5to 12, carbons in the alkyl chain. Such alkyl groups would be surfaceactive and would be desirable when the precursor is used to form surfaceactive peracids for oxidizing fat or oil based soils from substrates atrelatively low temperatures.

It is further highly preferred for R to be aryl and C₁₋₂₀ alkylaryl. Adifferent type of bleaching compound results when aromatic groups areintroduced onto the ester.

Alkyl groups are generally introduced onto the ester via an acidchloride synthesis discussed in Ser. Nos. 06/928,070 and 07/167,544.Fatty acid chlorides such as hexanoyl chloride, heptanoyl chloride,octanoyl chloride, nonanoyl chloride, decanoyl chloride and the likeprovide this alkyl moiety. Aromatic groups can be introduced viaaromatic acid chlorides (e.g., benzoyl chloride) or aromatic anhydrides(e.g., benzoic acid anhydride).

R' and R" are independently H, C₁₋₁₀ alkyl, aryl, C₁₋₁₀ alkylaryl, andsubstituted aryl. When R' and R" are both alkyl, aryl, alkylaryl,substituted alkyl, or mixtures thereof, preferably the total number ofcarbons of R'+R" does not exceed about either 20, more preferably doesnot exceed about 18. Preferably, when R' or R" are carbylene or arylene,the other is H (i.e., unsubstituted). Alkyl of about 1-4 are preferred.If substituted aryl, appropriate substituents include OH, SO₃ ⁻, and CO₂⁻ ; NR₃ ^(a) + (R^(a) is C₁₋₃₀ carbons, and preferably, two of R^(a) areshort chain (C₁₋₄) alkyls and one of R^(a) is a long chain alkyl(C₈₋₃₀). Appropriate counterions include Na⁺, K⁺, etc. and appropriatenegative counterions include halogen (e.g., Cl⁻), OH⁻ and methosulfate.It is preferred that at least one of R' and R" be H, and mostpreferably, both (thus forming methylene).

The parent application stressed the importance of the R' and R" alpha,alpha substituents on the carbylene of the acyl group. This is becausethe position of various substituents alpha to the proximal carbonyl isvery important to the activators.

The leaving group, as discussed above, is basically capable of beingdisplaced by perhydroxide anion in aqueous medium. Unlike prior artprecursors, the activator is not limited to leaving groups havingParticular solubility or reactivity criteria due to the reactiveness ofthe acyl of the inventive precursor. It is, however, preferred that theconjugate acid of the leaving group have a pK_(a) of between about 4 to20, more preferably, about 6 to 15.

Thus, the preferred leaving grouPs, none of which are meant to limit theinvention, include:

(a) phenol derivatives

(b) halides

(c) oxynitrogen leaving groups

(d) carboxylic acid (from a mixed anhydride)

(a) Phenol Derivatives

The phenol derivatives can be generically defined as: ##STR20## whereinY and Z are, individually H, SO₃ M, CO₂ M, SO₄ M, OH, halo substituent,OR¹, R², NR₃ ³ X, and mixtures thereof, wherein M is an alkali metal oralkaline earth counterion, R¹ of the OR¹ substituent is C₁₋₂₀ alkyl, R2is C₁₋₆ alkyl, R₃ ³ of the NR₃ ³ substituent is C₁₋₃₀ alkyl, X is acounterion therefor, and Y and Z can be the same or different.

The alkali metal counterions to sulfonate, sulfate or carbonate (all ofwhich are solubilizing groups) include K⁺, Li⁺ and most preferably, Na⁺.The alkaline earth counterions include Sr⁺⁺, Ca⁺⁺, and most preferably,Mg⁺⁺. Ammonium (NH₄ ⁺) and other positively charged counterions may alsobe suitable. The halo substituent can be F, Br or most preferably, Cl.When OR¹, alkoxy, is the substituent on the phenyl ring, R¹ is C₁₋₂₀,and the criteria defined for R on the acyl group apply. When R² is thesubstituent on the phenyl ring, it is a C₁₋₁₀ alkyl, with preferencegiven to methyl, ethyl, n-- and iso-propyl, n--, sec-- and tert-butyl,which is especially preferred. When --NR₃ ³ X, quaternary ammonium, isthe substituent, it is preferred that two of R³ be short chain alkyls ,most preferably, methyl) and one of the R³ longer chain alkyl (e.g.,C₈₋₃₀), with X, a negative counterion, preferably selected from halogen(Cl.sup. -, F⁻, Br⁻, I⁻), CH₃ SO₄ ⁻ (methosulfate), NO₃ ⁻, or OH⁻.

Especially preferred are phenol sulfonate leaving groups. A preferredsynthesis of phenol sulfonate esters which could be adapted for useherein is disclosed in Zielske, U.S. Pat. No. 4,735,740 commonlyassigned to The Clorox Company, incorporated herein by reference.

Non-limiting preferred phenol derivatives are: ##STR21##

(b) Halides

The halide leaving groups are quite reactive and actually are directlyobtained as the intermediates in the synthesis of the phenyl sulfonateand t-butylphenol esters. While halides include Br and F, Cl is mostPreferred. A non-limiting example is:

    --Cl (chloride)

(c) Oxynitrogen

The oxynitrogen leaving groups are preferred. In the co-pendingapplication entitled "Acyloxynitrogen Peracid Precursors," inventorAlfred G. Zielske, commonly assigned to The Clorox Company, Oakland,Calif., filed concurrently herewith, Ser. No. 06/928,065, filed Nov. 6,1986, incorporated herein by reference, a detailed description of thesynthesis of these leaving groups is disclosed. These oxynitrogenleaving groups are generally disclosed as --ONR⁵, wherein R⁵ comprisesat least one carbon which is singly or doubly bonded directly to N.

--ONR⁵ is more specifically defined as: ##STR22## wherein R⁶ and R⁷ areindividually H, C₁₋₂₀ alkyl, (which can be cycloalkyl, straight orbranched chain), aryl, or alkylaryl and at least one of R⁶ and R⁷ is notH. Preferably R⁶ and R⁷ are the same or different, and range from C₁₋₆.Oximes are generally derived from the reaction of hydroxylamine witheither aldehydes or ketones.

Non-limiting examples of an oxime leaving group are: (a) oximes ofaldehydes (aldoximes), e.g., acetaldoxime, benzaldoxime,propionaldoxime, butylaldoxime, heptaldoxime, hexaldoxime,phenylacetaldoxime, p-tolualdoxime, anisaldoxime, caproaldoxime,valeraldoxime and p-nitrobenzaldoxime; and (b) oximes of ketones(ketoximes), e.g., acetone oxime (2-propanone oxime), methyl ethylketoxime (2-butanone oxime), 2-pentanone oxime, 2-hexanone oxime,3-hexanone oxime, cyclohexanone oxime, acetophenone oxime, benzophenoneoxime, and cyclopentanone oxime.

Particularly preferred oxime leaving groups are: ##STR23##

Hydroxyimide leaving groups comprise: ##STR24## wherein R⁸ and R⁹ can bethe same or different, and are preferably straight chain or branchedC₁₋₂₀ alkyl, aryl, alkylaryl or mixtures thereof. If alkyl, R⁸ and R⁹can be partially unsaturated. It is especially preferred that R⁸ and R⁹are straight or branched chain C₁₋₆ alkyls, which can be the same ordifferent. R¹⁰ is preferably C₁₋₂₀ alkyl, aryl or alkylaryl, andcompletes a heterocycle. R¹⁰ includes the preferred structure ##STR25##wherein R¹¹ can be an aromatic ring fused to the heterocycle, or C₁₋₆alkyl (which itself could be substituted with water solubilizing groups,such as EO, PO, CO₂ ⁻ and SO₃ ⁻).

These esters of imides can be prepared as described in Greene,Protective Groups in Organic Synthesis, p. 183, (incorporated byreference) and are generally the reaction products of acid chlorides andhydroxyimides.

Non-limiting examples of N-hydroxyimide which will provide thehydroxyimide leaving groups of the invention include:N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxyglutarimide,N-hydroxynaphthalimide, N-hydroxymaleimide, N-hydroxydiacetylimide andN-hydroxydipropionylimide.

Especially preferred examples of hydroxyimide leaving groups are:##STR26##

Amine oxide leaving groups comprise: ##STR27##

In the first preferred structure for amine oxides, R¹² and R¹³ can bethe same or different, and are preferably C₁₋₂₀ straight or branchedchain alkyl, aryl, alkylaryl or mixtures thereof. If alkyl, thesubstituent could be partially unsaturated. Preferably, R¹² and R¹³ areC₁₋₄ alkyls and can be the same or different. R¹⁴ is preferably C₁₋₃₀alkyl, aryl, alkylaryl and mixtures thereof. This R¹⁴ substituent couldalso be partially unsaturated. It is most preferred that R¹² and R¹³ arerelatively short chain alkyl groups (CH₃ or CH₂ CH₃) and R¹⁴ ispreferably C₁₋₂₀ alkyl, forming together a tertiary amine oxide.

Further, in the second preferred amine oxide structure, R¹⁵ can be C₁₋₂₀alkyl, aryl or alkylaryl, and completes a heterocycle. R¹⁵ preferablycompletes an aromatic heterocycle of 5 carbon atoms and can be C₁₋₆alkyl or aryl substituted. R¹⁶ is preferably nothing, C₁₋₃₀ alkyl, aryl,alkylaryl or mixtures thereof. R¹⁶ is more preferably C₁₋₂₀ alkyl if R¹⁵completes an aliphatic heterocycle. If R¹⁵ completes an aromaticheterocycle, R¹⁶ is nothing.

Non-limiting examples of amine oxides suitable for use as leaving groupsherein can be derived from: pyridine N-oxide, trimethylamine N-oxide,4-phenyl pyridine N-oxide, decyldimethylamine N-oxide,dodecyldimethylamine N-oxide, tetradecyldimethylamine N-oxide,hexadecyldimethylamine N-oxide, octyldimethylamine N-oxide,di(decyl)methylamine N-oxide, di(dodecyl)methylamine N-oxide,di(tetradecyl)methylamine N-oxide, 4-picoline N-oxide, 3-picolineN-oxide and 2-picoline N-oxide.

Especially preferred amine oxide leaving groups include: ##STR28##

(d) Carboxylic Acids from Mixed Anhydrides

Carboxylic acid leaving groups have the structure ##STR29## wherein R¹⁷is C₁₋₁₀ alkyl, preferably C₁₋₄ alkyl, most preferably either CH₃ or CH₂CH₃ and mixtures thereof.

When R¹⁷ is C₁ and above, it is believed that the leaving groups willform carboxylic acids upon perhydrolytic conditions. Thus, when R¹⁷ isCH₃, acetic acid would be the leaving group; when CH₂ CH₃, propionicacid would be the leaving group, and so on. However, the foregoingtheory is non-binding and offers only one explanation for what may be avery complicated reaction.

Non-limiting examples of mixed anhydride esters include: ##STR30##

Advantages of the Stable Bleach Activator

As previously described in the parent application, U.S. Ser. No.06/928,070, the activator provides numerous advantages over the priorart. For one, the activator is not tied to critical ratios of hydrogenperoxide source to activator, as are the fatty acid esters of Chung etal., U.S. Pat. No. 4,412,934. Additionally, because the activatorpresents multiple acyl functionalities, it can provide more than onetype of peracid, thus boosting performance in laundering applications.For instance, a preferred activator, octanoyloxyacetate, phenolsulfonate ester, can give rise to three different peracids: ##STR31##

The prior art materials cannot provide these advantages.

For instance, one facially similar, but entirely inferior activator isdisclosed in Schirmann et al., U.S. Pat. No. 4,221,675. A product comingwithin Schirmann et al's disclosure was synthesized, alPha-octanoyl,N-acetylacetamide, and Perhydrolysis studies were conducted to see whatreactions were being generated. In conducting the study, it was assumedthat perhydrolytic attack on the compound could take Place at one or allor a combination of three sites: ##STR32##

Three moles of hydrogen peroxide per mole of activator (one per carbonylsite) were reacted with this alpha-octanoyloxy, N-acetylacetamide.

Tallying the reaction products via high performance liquidchromatography (HPLC) using an adaptation of the potentiometric methodsset forth in Isaakson et al, "Reaction Detector for LiquidChromatography with Electrochemical Generation and Detection of Excessof Bromine," J. Chromatography, Vo. 324, pp. 333 et seq. (1986), theresults were:

                  TABLE I                                                         ______________________________________                                        Perhydrolysis Profile.sup.1 of                                                octanoyloxy, N-acetylacetamide                                                                  pH                                                          Peracid/Product                                                                              Site     10.5    9.5    8.8                                    ______________________________________                                        Peroctanoic Acid                                                                             A        27.3%   8.60%  0.83%                                  Peroctanoyloxyacetic Acid                                                                    B         2.1%   0.59%  0.00%                                  Peracetic Acid C         9.1%   5.3%   0.20%                                  Octanoyloxyacetic Acid                                                                       hydro-   55.0%   n/a.sup.2                                                                            n/a.sup.2                                             lysis                                                                         at B                                                           ______________________________________                                         .sup.1 Assuming three perhydrolytic sites, 14 ppm A.O. theoretical maximu     yield. HPLC at 13 minutes.                                                    .sup.2 not available                                                     

Review of the above discloses that the major reaction of the compoundalpha-octanoyloxy, N-acetylacetamide is hydrolysis, not perhydrolysis.Additionally, primary sites for perhydrolysis are at a and c, meaningthat site b is very inefficient. This is to be compared with one of thepreferred activators, octanoyloxy acetic acid, phenyl sulfonate ester,which has the majority of perhydrolysis at site B, little at site A:

                  TABLE II                                                        ______________________________________                                         ##STR33##                                                                    Perhydrolysis Profile of.sup.1                                                Octanoyloxyacetic Acid, Phenyl Sufonate Ester                                                 pH                                                            Peracid/Product   10.5.sup.2                                                                           10.5.sup.3                                                                            9.5.sup.4                                                                           8.5.sup.5                              ______________________________________                                        Peroctanoic Acid   4%    10%      4%    3%                                    Peroctanoyloxyacetic Acid                                                                       59%    55%     62%   41%                                    Perglycolic Acid   5%    11%      3%    3%                                    Octanoyloxyacetic Acid                                                                          23%    15%     15%.sup.6                                                                           32%                                    ______________________________________                                         .sup.1 Date obtained from HPLC; 2:1 peroxide:precursor ratio; based on tw     minutes from start from perhydrolysis.                                        .sup.2 Initial precursor concentration: 0.8 mM                                .sup.3 Initial precursor concentration: 6.0 mM                                .sup.4 Initial precursor concentration: 6.0 mM                                .sup.5 Initial precursor concentration: 6.0 mM                                .sup.6 Estimated.                                                        

Nakagawa et al., U.S. Pat. No. 3,960,743, discloses contended bleachactivators of the structure: ##STR34## in which B is H or C₁₋₃ alkyl, Mis C₁₋₄ alkyl, H, or alkali metal salt. This structure can be dividedinto two categories: ( 1) when M is C₁₋₄ alkyl, n can be l, thusproviding an alkyl ester of acylglycolic acid; and (2) when M is H oralkali metal salt, n must be greater than l, thus the compound must bepolymeric.

In the case of (1), M completing an alkyl ester, it is clear that M doesnot function as a leaving group. Alkyl alcohols are not leaving groups.

In the case of (2), M is H or alkali metal salt, these again do notfunction as leaving groups.

In the case where M is H or alkali metal salt, a compound which isrepresentative of Nakagawa et al, namely, octanoyloxyacetic acid, wastested for perhydrolytic performance. (If placed in an alkaline medium,this acid would be neutralized, i.e., deprotonated, and would form thealkali metal salt. Thus, this compound is representative of either M isH or alkali metal salt.) Octanoyloxyacetic acid has the structure##STR35##

The compound can be synthesized as described in the parent application,Ser. No. 06/928,070, at pages 33-34 thereof.

In testing this representative compound, the following conditions wereused:

Octanoyloxyacetic Acid: 8.75×10⁻⁴ M (dissolved in 3 ml of 50/50vol./vol. dioxane/water)

Hydrogen Peroxide: 1.65×10⁻³ M

Temperature: 21° C.

PH: 10.5

Buffer: 0.02 M (NaCO₃ /NaHCO₃)

Thus, 1.9 moles of H₂ O₂ per mole of this "activator" were placed inaqueous solution.

Tallying the reaction products via high performance liquidchromatography (HPLC) using an adaptation of the potentiometric methodsset forth in Isaakson et al, "Reaction Detector for LiquidChromatography with Electrochemical Generation and Detection of Excessof Bromine," J. Chromatography. Vol. 324, pp. 333 et seq. (1986), theresults were:

                  TABLE III                                                       ______________________________________                                        Perhydrolysis Profile of Octanoyloxyacetic Acid                                                              Octanoyloxyacetic                              Time  Total A.O..sup.1                                                                           Peracid.sup.2                                                                             Acid.sup.3                                     (min.)                                                                              Concentration                                                                              Concentration                                                                             Concentration                                  ______________________________________                                         5    1.76 mM      N/D.sup.4   0.85 mM                                        10    1.52 mM      N/D.sup.4   0.84 mM                                        20    1.64 mM      N/D.sup.4   0.88 mM                                        ______________________________________                                         .sup.1 Total Active Oxygen ("AO") concentration (mM) determined by            iodide/thiosulfate titration using molybdate catalyst; includes H.sub.2       O.sub.2 and peracids.                                                         .sup.2 Peracid concentration (mM) determined by iodide/thiosulfate            titration after treatment with catalase enzyme to eliminate the hydrogen      peroxide.                                                                     .sup.3 Concentration (mM) measured by HPLC.                                   .sup.4 Not detected; additionally, no peracids were detected by HPLC          (detection limit is 0.001 mM).                                           

Thus, as seen from the above, neither Schirmann et al. nor Nakagawa etal. provide the benefits of the activators of the invention.

Stable Bleach Activator Granules

While it has been disclosed by Applicants in the parent application,that substituting solubilizing groups may improve the solubility andenhance the reactivity of the activators, the present invention concernscombining the activator with a suitable binding material in order toform granules which are stable upon storage and which form peracid moreefficiently.

The granules are formed by combining the hereinbefore-describedactivators with pliable binding materials having a melting completiontemperature of at least about 40° C. It is preferred to include a fillermaterial which can control solubility of the granule and for goodhandling characteristics.

1. Binder Material

The binder material is critical to the invention. It should be anorganic material which has a melting completion temperature (meltingpoint) above about 40° C., more preferably above about 50° C. Thematerial should not react with either the activator, or, if the granulesare combined with an oxidant-containing detergent, with the componentsof such detergent during storage thereof. The binder should ideallY havelow hygroscopicity, yet be soluble or dispersible in aqueous solution,preferably at low temperatures. The binder should also be able to form apaste or doughy mass suitable for forming noodles, and after Processing,granules. Workability, viscosity, pliability, and miscibility in water,of the binder should be optimal, depending on the process used.

Types of materials suitable for use include, without limitation:

Organic Materials

1. Nonionic Surfactants.

2. Anionic Surfactants.

3. Cationic Surfactants.

4. Film-forming polymers.

5. C₁₂ --C₁₈ Fatty acids or salts thereof.

6. C₁₂ --C₂₄ Aliphatic alchols.

7. Relatively low molecular weight polyethylene glycols (2,000-10,000).

8. Sodium alkyl glyceryl ether sulfonate (sodium coconut oil, fattyacids monoglyceric sulfonates and sulfates); sodium alkyl ethersulfonates; alkylphenol-ethylene oxide ether sulfate; and esters ofalpha-sulfonated fatty acid.

9. Acrylic acid, hydroxyacrylic acid, methacrylic acid Polymers;co-polymers of ethylene styrene and vinyl methyl ether (e.gs., Versicol& Gantrez).

10. Cellulose acetate esters, cellulose acetate sulfate, cellulosesulfates, hydroxyethyl cellulose sulfate, methylcellulose sulfate,hydroxypropylcellulose sulfate.

11. Starch, starch/ether.

12. Sodium carboxymethyl cellulose.

13. Polyvinyl alcohol.

14. Gelatin.

15. HPL (National Starch & Chemical Corp., (an amylopectin food starch).

16. Cross-linked pre-gelatinized amylope (e.g., Clearjel, NationalStarch & Chemical CorP.).

The binder material imparts physical integrity to the particle which isimportant in particle crush durability. Although organic binders arepreferred, certain silicates may also be suitable for use. Other bindersdisclosed in Chung et al., EP 106 634 (incorporated herein by reference)are suitable for use. The binder also aids in the dispersion of theparticle and solubilization of the precursor. Preferred binder materialswere selected from the following classes of compounds: Calsoft F90,Calsoft L40 and Biosoft D62 from the linear alkylbenzene sulfonates;Carbowax 3350, 4600 and 8000, from polyethylene glycols; Span 40 fromsubstituted sorbitans; Triton CF54 from alkyl aryl polyethoxy adducts;Pluronic F125 form block copolymers of propylene and ethylene oxide;Alfonic 1618-80, Brij-58, and Neodol 45-13 from ethoxylated alcohols;sodium palmitate from fatty acid salts; and polyacrylic acid. Of thesethe Calsoft materials, Alfonic 1618-80 and Carbowax 4600 (polyethyleneglycol, Mol wt. =4,600) were found to be most preferred. The especiallypreferred binding materials consist of a 50/50 wt./wt. combination ofCalsoft L40 (a C₁₁.5 linear alkyl benzene sulfonate, sodium salt, 40%active, from Pilot Chemical Co.) and Alfonic 1618-80 (a C₁₆₋₁₈ethoxylated alcohol, with about 10.7 moles of ethylene oxide per mole ofalcohol, 100% active, from Vista Chemicals); and Carbowax 4600 andCalsoft L40 in 50/50 wt. wt. mixture, base don actives.

2. Filler/Diluent

A filler or diluent can be used to control solubility of the granule andto assure optimal processibility of the noodle. The diluent also helpsin the dispersion of the precursor by allowing the particles to break upmore readily when placed into an aqueous medium. The nature of thediluent should be such that it does not react with the other componmentsof the particles, is readily soluble, not hygroscopic and can bepowdered to the same mesh size as the precursor. The filler is any inertsalt such as Na₂ SO₄, Na₂ CO₃, NaCl, boric acid, borax, and other alkalimetal salts. It is preferable that water-insoluble materials be limited,e.g., CaCO₃, MgCO₃, etc.

3. Forming the Granules

The activator, binder and diluent/filler are combined, usually withadditional water (although some binders, e.g., surfactants, are suppliedby manufacturers as aqueous solutions, so the amount of added water canbe limited or varied as needed) in order to form a workable paste ordoughy mass.

The process of Preference is referred to as extrusion, in which materialas hereinbefore described is processed into a doughy mass and extrudedthrough a dieplate or other sizing means to form long noodles. Suchnoodles are then dried and chopped or vibrated or otherwise formed intogranules. Alternatively, the granules could be formed by agglomerationor spray bed Process, both of which form a part of the invention.

The noodles are prepared by first dry mixing the solid components of theformulation, which includes activator, diluent, and optional colorant,to form an evenly distributed dry powder. This mixture is then added toa fluid hot melted binder or to a warm aqueous solution of binder toform a doughy mass. The doughy mass can be further moistened to aidprocessing by the addition of 2-15% water by weight of the mixture. Thesubstantially homogeneous mass is then extruded through a .25 mm-2 mmdiameter die hole. Noodle extrudate is then dried to a water content ofpreferably less than 3% by weight of the processed noodle. The driednoodles are then chopped down to lengths not greater than 5 mm.

By reference to FIG. 1, a flow diagram of the process, simplifieddescription of a non-limiting embodiment of the process can bedemonstrated. The dry components (activator, diluent and optionalcolorant) are dry-mixed to form a dry preblend 2. Secondly, the liquidcomponents (surfactants, polymers, i.e., binders, and water) are mixedto form a liquid preblend 4. These two product streams are added in amixer 6 which forms the doughy mass. The mass is passed through to anextruder 8. This can comprise an inverted-funnel-shaped hopper providedwith screws in the bottom thereof. The screws work the mass and channelit to a die plate, grate, or other means of reducing the mass size. Asthe mass is forced out of the die, it produces long "noodles," whichthen fall into a sizer 10. The sizer can be a shaker bed, which is avibrating bed which breaks the noodles up into the desired shapes andsizes of granules. The sizer could alternatively be a continuousconveyor or combined with a vibrator or with a spike to break up thenoodles, in which case the Process can be continuous (the conveYor couldcarry off the desired particles, while the fines could be recycled.) Thefines, particles less than about 0.1 mm in length, could be shaken offto a collector 12, which preferably recycles the fines to the extruder8. The granules could then be dried in a drier 16, then outputted to acollector 18, with fines again siphoned off via a fines collector 14,which Preferably recycles such fines. The finished granules 20 are thenpackaged or further taken via conveyor to be combined with the detergentbase.

4. The Granules

The granules have increased storage stability over unprocessedprecursor, good crush durability properties and dissolve readily in thewash water. The noodle particles preferably comprise from 50-99, morepreferably 80-97 percent precursor, from 0.5-25 more preferably 3-15,percent binder, from 0-25, more preferably 0-5, most Preferably 1-5,percent diluent and from 0-5 percent water based on the weight of theprocessed noodle. An oPtional colorant can also be present in the noodlein the range of from 0-5 percent by weight of the processed noodle. Allingredients of this particle composition are evenly distributedthroughout the particle.

The granule size is an important factor in storage stability andsolubility of the particle. It is preferred that the noodles have adiameter in the range of 2 to .25, more preferablY 1.5 to 0.3, mostpreferably 1.0 to 0.5 mm. Optimally, they will be 0.75 mm in diameter.The length of the particle is preferred to be from 0.1 to 5 mm, morepreferably 0.5 to 3 mm long. The particles are preferably cylindrical inshape. Alternatively, they may be spherical, with the preferreddiameters given above.

In the granules, the proportions of ingredients should be preferablybetween 99:0.5:0.5 to 50:25:25 activator: binder: diluent, morepreferably 98:1:1-75:12.5:12.5. High amounts of activator are desirablein order to enhance the finished product's performance and to reduce theoverall percentage of activator granules in the detergent for costefficiency. The particles should dissolve in water within about 10minutes at 21° C.

5. The Detergent Compositions

The activator granules of the invention are combined with a detergentbase, said base comprising:

builders; and

a surfactant selected from the group consisting of anionic, nonionic,cationic, amphoteric, zwitterionic surfactants, and mixtures thereof;and

a bleach-effective amount of a source of hydrogen peroxide to interactwith the activator granules.

Each of these comPonents, and adjunct materials suitable for use hereinare further discussed below:

6. Builders

The builders are typically alkaline builders, i.e., those which inaqueous solution will attain a pH of 7-14, preferably 9-12. Examples ofinorganic builders include the alkali metal and ammonium carbonates(including sesquicarbonates and bicarbonates), phosphates (includingorthophosphates, tripolyphosphates and tetrapyrophosphates),aluminosilicates (both natural and synthetic zeolites), and mixturesthereof. Carbonates are especially desirable for use in this inventionbecause of their high alkalinity and effectiveness in removing hardnessions which may be present in hard water, as well as their low cost.Carbonates be used as the Predominant builder. Silicates (Na₂ O:SiO₂,modulus of 4:1 to 1:1, most preferably about 3:1 to 1:1) can also beused. Silicates, because of their solubity in water and ability to forma glassy matrix, can also advantageously used as a binder for thedetergent.

Organic builders are also suitable for use, and are selected from thegroup consisting of the alkali metal and ammonium sulfosuccinates,polyacrylates, polymaleates, copolymers of acrylic acid and maleic acidor maleic anhydride, citrates and mixtures thereof.

7. Fillers/Diluents

The same materials as used in the manufacture of the granules can beused herein as fillers for the detergent. Salts such as NaCl, Na₂ SO₄,and borox, are preferred. Organic diluents, such as sugar, are possible.

8. Surfactants

Particularly effective surfactants appear to be anionic surfactants.Examples of such anionic surfactants may include the ammonium,substituted ammonium (e.g., mono--, di--, and tri-ethanolammonium),alkali metal and alkaline earth metal salts of C₆ -C₂₀ fatty acids androsin acids, linear and branched alkyl benzene sulfonates, alkylsulfates, alkyl ether sulfates, alkane sulfonates, olefin sulfonates,hydroxyalkane sulfonates, fatty acid monoglyceride sulfates, alkylglyceryl ether sulfates, acYl sarcosinates and acyl N-methyltaurides.Preferred are aromatic sulfonated surfactants. Of particular preferenceare linear and branched C₆₋₁₈ alkyl benzene sulfonates, both the saltsthereof as well as the acidic form. Most preferred are the acidic alkylbenzene sulfonates such as Biosoft S100 and S130, with the latterespeciallY preferred.

Other preferred surfactants of use include linear ethoxylated alcohols,such as those sold by Shell Chemical ComPany under the brand nameNeodol. Other suitable nonionic surfactants can include other linearethoxylated alcohols with an average length 6 to 16 carbon atoms andaveraging about 2 to 20 moles of ethylene oxide per mole of alcohol;linear and branched, primary and secondary ethoxylated, propoxylatedalcohols with an average length of about 6 to 16 carbon atoms andaveraging 0-10 moles of ethylene oxide and about 1 to 10 moles ofpropylene oxide per mole of alcohol; linear and branched alkylphenoxy(Polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, withan average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30moles of ethylene oxide per mole of alcohol; and mixtures thereof.

Further suitable nonionic surfactants may include polyoxyethylenecarboxylic acid esters, fatty acid glycerol esters, fatty acid andethoxylated fatty acid alkanolamides, certain block copolymers ofPropylene oxide and ethylene oxide, and block polymers of propyleneoxide and ethylene oxide with propoxylated ethylene diamine. Alsoincluded are such semi-Polar nonionic surfactants like amine oxides,phosphine oxides, sulfoxides, and their ethoxylated derivatives.

Suitable cationic surfactants may include the quaternary ammoniumcompounds in which typically one of the groups linked to the nitrogenatom is a C₁₂ -C₁₈ alkYl group and the other three groups are shortchained alkyl grouPs which may bear substituents such as phenyl groups.

Further, suitable amphoteric and zwitterionic surfactants which containan anionic water-solubilizing group, a cationic group and a hydrophobicorganic group may include amino carboxylic acids and their salts, aminodicarboxylic acids and their salts, alkylbetaines, alkylaminopropylbetaines, sulfobetaines, alkyl imidazolinium derivatives,certain quaternary ammonium compounds, certain quaternary phosphoniumcompounds and certain tertiary sulfonium compounds. Other examples ofpotentially suitable zwitterionic surfactants can be found described inJones, U.S. 4,005,029, at columns 11-15, which are incorporated hereinby reference.

Further examples of anionic, nonionic, cationic and amphotericsurfactants which may be suitable for use in this invention are depictedin Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition,Volume 22, pages 347-387, and McCutcheon's Detergents and Emulsifiers.North American Edition, 1983, which are incorporated herein byreference.

As mentioned hereinabove, other common detergent adjuncts may be addedif a bleach or detergent bleach product is desired. If, for example, adetergent composition is desired, the following ranges (weight %) appearpracticable:______________________________________0.5-50.0% HydrogenPeroxide Source0.05-25.0% Precursor1.0-50.0% Surfactant1.0-50.0%Builder5.0-99.9% Filler, stabilizers, dyes, Fragrances, brighteners,etc.______________________________________

9. Hydrogen Peroxide Source

The hydrogen peroxide source may be selected from the alkali metal saltsof percarbonate, perborate, persilicate and hydrogen peroxide adducts.

Most Preferred are sodium Percarbonate, and sodium perborate mono- andtetrahydrate. Other Peroxygen sources may be possible, such as alkalineearth and alkali metal Peroxides, monopersulfates and monoperphosphates.

The range of peroxide to activators is preferably determined as a molarratio of peroxide to activator. Thus, the range of peroxide to eachactivator is a molar ratio of from about 1:1 to 20:1, more preferablyabout 1:1 to 10:1 and most preferably about 1:1 to 5:1. This is also thedefinition of a bleach effective amount of the hydrogen peroxide source.It is preferred that this activator Peroxide composition provide about0.5 to 100 ppm peracid A.O., and most preferably about 1 to 50 ppmperacid A.O., and most preferably about 1 to 20 ppm peracid A.O., inaqueous media.

A description of, and explanation of, A.O. measurement is found in thearticle of Sheldon N. Lewis, "Peracid and Peroxide Oxidations," In:Oxidation. 1969, pp. 213-258, which is incorporated herein by reference.Determination of the peracid can be ascertained by the analyticaltechniques taught in Organic Peracids, (Ed. by D. Swern), Vol. 1, pp.501 et seq. (Ch.7) (1970), incorporated herein by reference.

10. Chelating Agents

In some of the compositions herein, it is especially Preferred toinclude a chelating agent, most preferably, an aminopolyphosphonate.These chelating agents assist in maintaining the solution stabilitY ofthe activators in order to achieve optimum perhydrolysis. In thismanner, they are acting to chelate heavy metal ions, which causecatalyzed decomposition of the in situ formed peracid, although this isa non-binding theory of their action and not limiting to Applicants. Thechelating agent is selected from a number of known agents which areeffective at chelating heavy metal ions. The chelating agent should beresistant to hydrolysis and rapid oxidation by oxidants. Preferably, itshould have an acid dissociation constant (pK_(a)) of about 1-9,indicating that it dissociates at low pH's to enhance binding to metalcations. The most preferred chelating agent is an aminopolyphosphonatewhich is commercially available under the trademark Dequest, fromMonsanto Company. Examples thereof are Dequest 2000, 2041 and 2060. (Seealso Bossu, U.S. Pat. No. 4,473,507, column 12, line 63 through column13, line 22, incorporated herein by reference). A polyphosphonate, suchas Dequest 2010, is also suitable for use. Other chelating agents, suchas ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid(NTA) may also be suitable for use. Mixtures of the foregoing may besuitable. Effective amounts of the chelating agent range from 1-1,000,more preferably 5-500, most preferably 10-100 ppm chelating agent, inthe wash liquor.

11. Adjuncts

The standard detergent adjuncts can be included in the presentinvention.

These include enzymes are especially desirable adjunct materials inthese detergent products. However, it may be preferred to include anenzyme stabilizer.

Proteases are one especially Preferred class of enzymes. They areselected from acidic, neutral and alkaline Proteases. The terms"acidic," "neutral," and "alkaline," refer to the pH at which theenzymes activity are optimal. Examples of neutral proteases includemmilezyme (available from Miles Laboratory) and trypsin, a naturallyoccurring protease. Alkaline proteases are available from a wide varietyof sources, and are typically produced from various microorganisms(e.g., Bacillis subtilisis). Typical examples of alkaline proteasesinclude Maxatase and Maxacal from International BioSynthetics, Alcalase,Savinase and Esperase, all available from Novo Industri A/S. See alsoStanislowski et al., U.S. Pat. No. 4,511,490, incorporated herein byreference.

Further suitable enzymes are amylases, which arecarbohydrate-hydrolyzing enzymes. It is also Preferred to includemixtures of amylases and proteases. Suitable amylases include Rapidase,from Societe Rapidase, Milezyme from Miles Laboratory, and Maxamyl fromInternational BioSynthetics.

Still other suitable enzymes are cellulases, such as those described inTai, U.S. Pat. No. 4,479,881, Murata et al., U.S. Pat. No. 4,443,355,Barbesgaard et al., U.S. Pat. No. 4,435,307, and Ohya et al., U.S.3,983,082, incorporated herein by reference.

Yet other suitable enzymes are lipases, such as those described inSilver, U.S. Pat. No. 3,950,277, and Thom et al., U.S. 4,707,291,incorporated herein by reference.

The hydrolytic enzyme should be present in an amount of about 0.01-5%,more preferably about 0.01-3%, and most preferably about 0.1-2% byweight of the detergent. Mixtures of any of the foregoing hydrolases aredesirable, especially protease/amylase blends.

Additionally, optional adjuncts include dyes, such as Monastral blue andanthraquinone dyes (such as those described in Zielske, U.S. Pat. No.4,661,293, and U.S. Pat. No. 4,746,461).

Pigments, which are also suitable colorants, can be selected, withoutlimitation, from titanium dioxide, ultramarine blue (see also, Chang etal., U.S. Pat. No. 4,708,816), and colored aluminosilicates.

Fluorescent whitening agents are still other desirable adjuncts. Theseinclude the stilbene, styrene, and naphthalene derivatives, which uponbeing impinged by ultraviolet light, emit or fluoresce light in thevisible wavelength. These FWA's or brighteners are useful for improvingthe appearance of fabrics which have become dingy through repeatedsoilings and washings. Preferred FWA's are Tinopal 5BMX-C and TinopalRBS, both from Ciba Geigy A.G., and Phorwite RKH, from Mobay Chemicals.Examples of suitable FWA's can be found in U.S. Pat. Nos. 1,298,577,2,076,011, 2,026,054, 2,026,566, 1,393,042; and U.S. Pat. Nos.3,951,960, 4,298,290, 3,993,659, 3,980,713 and 3,627,758, incorporatedherein by reference.

Anti-redeposition agents, such as carboxymethylcellulose, arepotentially desirable. Next, foam boosters, such as appropriate anionicsurfactants, may be appropriate for inclusion herein. Also, in the caseof excess foaming resulting from the use of certain surfactants,anti-foaming agents, such as alkylated polysiloxanes, e.g.,dimethylpolysiloxane, would be desirable. Fragrances are also desirableadjuncts in these compositions, although the activators herein have muchlower odor than the fatty acid esters such as those in Chung et al.,U.S. Pat. No. 4,412,934.

The additives may be present in amounts ranging from 0-50%, morepreferably 0-30%, and most preferablY 0-10%. In certain cases, some ofthe individual adjuncts may overlap in other categories. However, thepresent invention contemPlates each of the adjuncts as Providingdiscrete performance benefits in their various categories. TheEXPERIMENTAL section below demonstrates the advantages of the inventivebleach activators and the detergents containing them.

EXPERIMENTAL

                  TABLE IV                                                        ______________________________________                                        Bleach Activator Granules                                                     Wt. %        Component                                                        ______________________________________                                        90           Precursor                                                        2.5          Binder, C.sub.16-18 ethoxylated                                               alcohol (Alfonic 1618-80 from Vista                                           Chemical Co.).                                                   2.5          Binder, C.sub.12 sodium alkyl aryl                                            sulfonate (Calsoft L40 from Pilot                                             Chemical Co.), on an actives basis.                              5            Diluent, can be any inert salt such                                           as Na.sub.2 SO.sub.4, Na.sub.2 CO.sub.3, NaCl,                                etc.                                                             ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        Detergent Formulation                                                         COMPONENT           Wt %                                                      ______________________________________                                        Na Tripolyphosphate 33.21                                                     HLAS                11.29                                                     Na Perborate Monohydrate                                                                          7.46                                                      Na.sub.2 CO.sub.3   40.40                                                     Silicate            4.98                                                      Moisture            2.66                                                                          100.00                                                    ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                        Detergent + Activator Formulation                                             Component           Wt. %                                                     ______________________________________                                        Na Tripolyphosphate 27.16                                                     HLAS (Biosoft S130) 9.23                                                      Na Perborate Monohydrate                                                                          6.10                                                      Na.sub.2 CO.sub.3   33.04                                                     Silicate            4.07                                                      Activator Granules  8.94                                                      Na.sub.2 SO.sub.4   6.74                                                      Alcosperse.sup.1    0.32                                                      Ultramarine Blue.sup.2                                                                            0.15                                                      FWA.sup.3           0.32                                                      Dequest 2006.sup.4  0.50                                                      Savinase.sup.5      0.91                                                      Fragrance           0.20                                                      Moisture            2.32                                                                          100.00                                                    ______________________________________                                         .sup.1 Polyacrylic Acid Binder, Alco Company.                                 .sup.2 Colorant                                                               .sup.3 Fluorescent whitening agent.                                           .sup.4 Chelating agent, Monsanto Company.                                     .sup.5 Protease enzyme, Novo Industri A/S.                               

Solubility and Crush Durability

The results in TABLE VII show the solubility index and crush durabilityfor several noodle compositions. The solubility index is defined as thetime in minutes required for a 0.2 g sample to completely dissolve in500 mL water at about 21° C. under constant stirring to yield a 2 cmvortex in a 1 liter beaker. The crush durability factor is the weight ingrams required to crush a 2 mm (length) granule between glass plates.

                  TABLE VII                                                       ______________________________________                                        Granules and Their Solubility Index and Crush Durability                                                      Solu-                                                   % Ac-   %       % Di- bility                                                                              Crush Factor                            Binder    tivator Binder  luent (Mins.)                                                                             (in grams)                              ______________________________________                                        Alfonic.sup.1                                                                           90.sup.2                                                                              10      0     5.23  40                                      1618-80   85.sup.2                                                                              15      0     3.88  63                                                80.sup.2                                                                              20      0     3.75  81                                                80.sup.2                                                                              15      5     3.4   55                                      Calsoft F90.sup.3                                                                       100.sup.2                                                                              0      0     10.0  <40                                               90.sup.2                                                                              10      0     2.1   40                                                85.sup.2                                                                              15      0     1.5   40                                                80.sup.2                                                                              20      0     2.0   40                                      50/50 Blend                                                                             90.sup.6                                                                               5      5     3.0   111                                     PEG 4600.sup.5 /                                                              Calsoft L40.sup.4                                                             50/50 Blend                                                                             90.sup.6                                                                               5      5     3.5   76                                      Alfonic.sup.1                                                                 1618-80/Calsoft                                                               L40.sup.4                                                                     ______________________________________                                         .sup.1 Nonionic surfactant, Vista Chemical Company.                           .sup.2 Activator is sodium octanoyloxyacetate, phenol sulfonate ester.        .sup.3 Anionic surfactant, Pilot Chemical Company, 90% active.                .sup.4 Anionic surfactant, Pilot Chemical Company, 40% active.                .sup.5 Polyethylene glycol (M.Wt. = 4,600), Union Carbide.                    .sup.6 Activator is sodium nonanoyloxyacetate, phenol sulfonate ester.   

Perhydrolysis and Storage Stability

The following granular dry bleaching compositions wereprepared:______________________________________Component Wt. inGrams______________________________________Na Perborate Monohydrate0.175 g (28 ppm A.O.)Na₂ CO₃ 1.200 gActivator gram amount equivalent to14 ppm(via granule or A.O.theoreticalPowder)______________________________________

The perhydrolysis profiles of the above bleach compositions (see TABLEIX, below) were carried out in the presence of Tide® (Procter & GambleCompany) detergent. The composition (approximate) of this detergent isshown below in TABLE VIII.

                  TABLE VIII                                                      ______________________________________                                        Composition of Tide ® Detergent                                           Component          Wt. %                                                      ______________________________________                                        Na.sub.2 CO.sub.3  14.7                                                       Na Tripolyphosphate                                                                              37.9                                                       [Na.sub.2 O]SiO.sub.2                                                                            4.0                                                        Na LAS             4.0                                                        Na AEOS            13.0                                                       Tinopal AMS (brightener)                                                                         0.21                                                       Water (moisture)   5.5                                                        Na.sub.2 SO.sub.4  20.8                                                                          100.00%                                                    ______________________________________                                    

Although this particular detergent base is used, other anionic ornonionic based detergents could be utilized as well.

The active oxygen profiles were obtained in the following manner: Thebleaching compositions were placed in 1,000 mL water 21.7° C., at 100ppm hardness (3/1 Ca⁺² /Mg⁺²), 1.5 mMol. NaHCO₃, with the detergentcontent at 1.287 g/L. The solution PH was adjusted to 10.5. The waterwas stirred at a rate so as to yield a 3cm vortex, in a standard 2 literbeaker, and the amount of active oxygen (A.O.) from peracid generatedwas determined iodometrically.

The results are shown in TABLE IX below, which demonstrate the benefitof using a granulated activator over the powdered activator, which wasclaimed in the parent application, Ser. No. 6/928,070. The granulatedactivator disperses more rapidly than the powdered activator, thusyielding a higher active oxygen level over a longer Period of time.

                  TABLE IX                                                        ______________________________________                                        Perhydrolysis Profile of Granulated                                           versus Powdered Activator                                                             % A.O. of theoretical @ various times (minutes)                       Example   t = 2        t = 6   t = 12                                         ______________________________________                                        Granule.sup.1                                                                           93           84      81                                             Powder.sup.2                                                                            45           71      82                                             ______________________________________                                         .sup.1 Granule was octanoyloxyacetate, phenol sulfonate ester, 90%, with      linear C.sub.11.5 alkylbenzene sulfonate, sodium salt, 10%.                   .sup.2 Powder was 100% octanoyloxyacetate, phenol sulfonate ester.       

Storage stability of dry bleach compositions containing the activatorwere determined under the following conditions: The compositions wereplaced in open glass vials and stored in a storage room which maintaineda constant temperature of about 32° C. and a relative humidity of about85%. After storage, the samples were measured for their activatorcontent by determining the yield of peracid A.O. in solution at six andtwelve minutes.

The percent activator of various samples after storage are shown inTABLE X.

                  TABLE X                                                         ______________________________________                                        Storage Stability in Open Glass Vials                                         32° C., 85% relative humidity                                                    % of original A.O. remaining                                                  Time in days                                                        Example     t = 0   t = 2     t = 7 t = 10                                    ______________________________________                                        Activator.sup.1 /                                                                         100     100       79    66                                        LAS.sup.2, 90/10                                                              Activator   100      76        9     5                                        (Powder)                                                                      ______________________________________                                         .sup.1 Octanoyloxyacetate, phenol sulfonate ester.                            .sup.2 linear C.sub.11.5 alkyl benzene sulfonate.                        

The results in TABLE X show that granulated activator is significantlymore storage stable than the powdered activator. After ten days storage,the granules exhibit a 44% A.O. loss, while the powder experiences about95% A.O. loss.

In the test below, storage stability of the noodled/granulated activatorwas compared against the powdered activator. The conditions were: 37°C., 70% relative humidity stored in an anionic (phosphate) base (see,e.g., the formulation of TABLE VI, above). The granules contained 90%nonanoyloxyacetate, phenol sulfonate ester; 5% Na₂ SO₄, and 5% binder(LAS and Carbowax 8000, Caroowax 4600, Alfonic 1618-80, each at 50/50wt./wt.).

                  TABLE XI                                                        ______________________________________                                        % A.O. yield of theoretical                                                   Binder        t = 0    t = 1 week                                                                              t = 2 weeks                                  ______________________________________                                        Carbowax 8000/LAS.sup.1                                                                     88%      83%       73%                                          Carbowax 4600/LAS.sup.1                                                                     88%      83%       73%                                          Alfonic       83%      80%       73%                                          1618-80/LAS.sup.1                                                             Powdered      63%      25%        0%                                          Activator                                                                     ______________________________________                                         .sup.1 LAS = Calsoft L40, Pilot Chemical Co.                             

Further tests were conducted comparing the granulated/noodled activatoragainst the powdered activator, but this time, as a detergentcomposition. In this case, the activator evaluated wasnonanoyloxyacetate, phenol sulfonate ester. The data were obtained inthe presence of the detergent formulation of TABLE V above. 1.4 g of thedetergent was added to 1,000 mL of water at 21° C. in a 2 liter beakerand stirred at a rate so as to yield a 3 cm vortex. The results arereported below, in TABLE XII.

                  TABLE XII                                                       ______________________________________                                        Perhydrolysis Profile of Noodled                                              Activator versus Powdered Activator                                                    % A.O. of theoretical at                                                      various times (t) in days                                            Sample     t = 4        t = 8   t = 12                                        ______________________________________                                        Activator.sup.1                                                                          88           88      78                                            Activator.sup.2                                                                          62           66      56                                            (Powder)                                                                      ______________________________________                                         .sup.1 Nonanoyloxyacetate, phenol sulfonate ester, 90% (as produced),         granulated with Calsoft L40, 2.5%, PEG 4600, 2.5%, sodium sulfate             (filler), 5%.                                                                 .sup.2 Nonanoyloxyacetate, phenol sulfonate ester, 100% (as produced).   

Further experiments conducted tested the performance of particularsurfactants in the detergent base with which the activator granules werecombined. Surprisingly, Applicants discovered that performances ofcertain long chain linear alkyl benzene sulfonates demonstrably improvedcleaning performance.

                  TABLE XIII                                                      ______________________________________                                        Chain length Distributions                                                             C.sub.10                                                                           C.sub.11                                                                              C.sub.12                                                                             C.sub.13                                                                            C.sub.14                                                                           Mol. Wt.                              ______________________________________                                        1. Biosoft S130                                                                          --     --      17%  50%   28%  340                                 2. Biosoft S100                                                                          20%    43%     32%   4%    1%  316                                 ______________________________________                                    

A nonphosphate detergent having the formulation as in TABLE XIV belowused surfactants 1 and 2 shown in TABLE XIII in the detergent base.These two examples were tested in wash water at about 21° C., 100 ppmhardness and the results in TABLE XV.

                  TABLE XIV                                                       ______________________________________                                        Nonphosphate Detergent + Activator Formulation                                Component            Wt. %                                                    ______________________________________                                        Na.sub.2 CO.sub.3    61.13                                                    HLAS                 11.34                                                    Na Perborate Monohydrate                                                                           7.49                                                     Silicate             6.48                                                     Activator Noodle     9.97                                                     Minors, including Na.sub.2 SO.sub.4                                                                3.59                                                     UMB, Enzyme, Moisture, etc.                                                                        100.00                                                   ______________________________________                                    

                  TABLE XV                                                        ______________________________________                                        Performance Comparison                                                        ______________________________________                                                     Soil/Fabric                                                                   % Soil Removal (E)                                                              Sebum on  Sebum on  Sebum on                                   Surfactant     Cotton    Polyester Polycotton                                 ______________________________________                                        Biosoft S130   71.9      92.6      81.6                                       Biosoft S100   62.2      73.8      69.1                                       LSD.sub.(t-test)                                                                              7.6       3.9       9.8                                       (95% confidence)                                                                             Average Scores For % S.R.                                                     on all Fabrics                                                 Biosoft S130   82.0                                                           Biosoft S100   68.4                                                           LSD.sub.(t-test)                                                                              4.4                                                           (95% confidence)                                                              ______________________________________                                    

The above data demonstrate that selection of surfactant can have asignificant effect on performance in detergent compositions containingthe inventive activator granules. Thus, it has been shown that longerchain anionic sufactants are especially desirable for implementation inApplicants' detergent systems.

In another test, the effect on performance is reviewed when sodiumperborate tetrahydrate is used as the oxidant, the surfactant chainlength is varied, and the builder system is non-phosphate. Theformulation in TABLE XIV, above, was used, with conditions of: perboratetetrahydrate crystals with particle size of U.S. mesh grade 30; 21° C.,100 ppm water hardness; and nonphosphate builder system (pH 10-10.5).

The results are shown in TABLE XVI.

                  TABLE XVI                                                       ______________________________________                                        % A.O. of peroxide yield at 12 minutes                                        Surfactant  Perborate 4H.sub.2 O.sup.1                                                                 Perborate 1H.sub.2 O.sup.2                           ______________________________________                                        Biosoft S130                                                                              31%          95%                                                  Biosoft S100                                                                              91%          95%                                                  Neodol 25-9 95%          95%                                                  ______________________________________                                         .sup.1 Sodium perborate tetrahydrate.                                         .sup.2 Sodium perborate monohydrate.                                     

The above results demonstrate that in a non-phosphate system, the chainlength of the surfactant can influence solubility of the perboratetetrahydrate, when the surfactant is anionic. Further, the effect is notinfluenced by pH in the 9.8-11.0 range, water hardness (0-200 ppm), andtemperature below 32° C.

Because of this effect, it is preferred to use perborate monohydrate ina non-phosphate system which, as shown in TABLE XVI, is soluble.

In yet another test below, the solubility difference between thephosphate detergent formulation containing sodium perborate monohydratein TABLE VI and an identical formulation containing sodium perboratetetrahydrate were compared. The amount of particulate residue collectedon a black swatch after filtering the wash solution therethroughindicates the degree of solubility of the respective formulations.

The procedure for determining detergent residue (meant to simulatescaled-down misuse conditions) is as follows: 10 g detergent is added toa 2 liter beaker containing 1,000 mL water at about 21° C. and stirredat a rate so as to yield a vortex of about 2-3 cm. After a time of tenminutes, the solution is filtered onto a black cloth (which has beenpreviously weighed). The cloth and the undissolved particles arecollected and dried. The dried cloth is then re-weighed to determine theamount of undissolved particles.

                  TABLE XVII                                                      ______________________________________                                        Detergent Solubility                                                          Example      Residue (grams)                                                  ______________________________________                                        A.sup.1      0.011                                                            B.sup.2      0.293                                                            ______________________________________                                         .sup.1 Detergent formula described in TABLE VI, above.                        .sup.2 Detergent formula listed in TABLE VI, with sodium perborate            tetrahydrate substituted for sodium perborate monohydrate.               

The above test results reported in TABLE XVII demonstrate that when thesurfactant used is C₁₂₋₁₄ HLAS, in a non-phosphate system, it ispreferred to use perborate monohydrate as the peroxide source in orderto reduce residual undissolved particles.

The next experiments show the effect of heavy metal ions on solutionstability of the in situ formed peracid from the inventive activatorgranules. Surprisingly, the use of an amino-polyphosphonate chelatingagent reduced loss of peracid formed in solution when heavy metalcations were present. Tri(methylene phosphonic acid) amine (Dequest 2000manufactured by Monsanto) was used as the chelating agent. Its effect onperacid decomposition in the presence of Cu⁺⁺ ion was measured bydissolving 4.5 g of the detergent composition shown in TABLE VI intothree liters of water containing 100 ppm hardness (3:1 Ca⁺² :mg⁺²) andthe concentration of copper shown in Table XVIII. The compositioncontained nonanoyloxyacetate phenol sulfonate ester as a powder.

                  TABLE XVIII                                                     ______________________________________                                        Average ppm.sup.1 of A.O. 4, 8, and 12 minutes                                Example                                                                              Avg. ppm.sup.1, A.O.                                                                       ppb.sup.2 Cu.sup.++                                                                      ppm.sup.1 Dequest 2000                         ______________________________________                                        1      2.7           0         0                                              2      2.0           50        0                                              3      1.3          100        0                                              4      0.9          250        0                                              5      2.6          250        10                                             ______________________________________                                         .sup.1 ppm = parts per million.                                               .sup.2 ppb = parts per billion.                                          

Table XVIII clearly demonstrates that heavy metal cations, e.g., copperion, decompose the peracid formed form the activator and that achelating agent (Dequest® 2000) prevents this copper ion catalyzeddecomposition.

The invention is further exemplified in the claims which follow.However, the invention is not limited thereby, and obvious embodimentsand equivalents thereof are within the claimed invention.

We claim:
 1. Stable bleach activator granules comprising:(a) a peroxygenbleach activator having the structure: ##STR36## wherein R is C₁₋₂₀branched or straight chain alkyl, alkoxylated alkyl, cycloalkyl,alkenyl, aryl, substituted aryl, alkylaryl; R' and R" are independentlyH, C₁₋₄ alkyl, aryl; and L is a leaving group selected from the groupconsisting of: ##STR37## wherein Y and Z are individually H, SO₃ M, CO₂M, OH, halo substituent, OR¹, NR³ ₃ X, and mixtures thereof, wherein Mis an alkali metal or alkaline earth metal counterion, R¹ of OR¹ isC₁₋₂₀ alkyl, R² is C₁₋₆ alkyl, R³ of NR³ ₃ is C₁₋₃₀ alkyl and X is acounterpart ion thereto, and Y and Z can be the same or different;(ii)halide; (iii) --ONR⁴, wherein R⁴ contains at least one carbon which issingly or doubly bonded directly to N; (iv) ##STR38## wherein R⁵ is aC₁₋₂₀ alkyl; and (v) mixtures thereof; (b) a pliable binding materialselected from materials having a melting completion temperature ofgreater than about 40° C.; and (c) optionally, a filler material.
 2. Thebleach activator granules of claim 1 wherein the proportions of a:b:crange from about (c) 99:0.5:0.5 to about 50:25:25.
 3. The bleachactivator granules of claim 1 wherein the activator of (a) has anleaving group, L, the conjugate acid whereof has a pK_(a) of about 4 to20.
 4. The bleach activator granules of claim 1 wherein the pliablebinding material of (b) is selected from the group consisting of anionicsurfactants, nonionic surfactants, water soluble organic polymers, waterdispersible organic polymers, and mixtures thereof.
 5. The bleachactivator granules of claim 1 wherein the filler material of (c) is aninorganic or organic filler.
 6. The bleach activator granules of claim 5wherein the filler material is an inorganic filler selected from alkalimetal and alkaline earth sulfates and chlorides.
 7. The bleach activatorgranules of claim 1 wherein the activator has the structure ##STR39##wherein R is C₁₋₂₀ alkyl.
 8. The bleach activator granules of claim 7wherein the activator has the structure ##STR40## and Y and Z areseparately selected from H, So₃ M, CO₂ M, SO₄ M, OH, halo substituent,OR¹, R², NR₃ ³ X, and mixtures counterion, R¹ of OR¹ is C₁₋₂₀ alkyl, R²is C₁₋₆ alkyl, R³ of NR₃ ³ is C₁₋₂₀ alkyl, and X is a counterpart ionthereto, and Y and Z can be the same or different.
 9. The bleachactivator granules of claim 8 wherein the activator has the structure:##STR41##
 10. The bleach activator granules of claim 9 wherein theactivator has the stucture ##STR42##
 11. The bleach activator granulesof claim 9 wherein the activator has the structure ##STR43##
 12. Thebleach activator granules of claim 9 wherein the activator has thestructure ##STR44##
 13. The bleach activator granules of claim 9 whereinthe activator has the structure ##STR45##
 14. The bleach activatorgranules of claim 9 wherein the activator has the structure ##STR46##15. The bleach activator granules of claim 9 wherein the activator hasthe structure ##STR47##
 16. The bleach activator granules of claim 1further comprising (d) a bleach-effective amount of a source of hydrogenperoxide.
 17. The bleach activator granules of claim 16 wherein saidsource of hydrogen peroxide is selected from the group consisting ofalkali metal perborates, alkali metal percarbonates, hydrogen peroxideadducts and mixtures thereof.
 18. Stable bleach activator granulescomprising:(a) a peroxygen bleach activator having the structure##STR48## wherein R is C₁₋₂₀ branched or straight chain alkyl,alkoxylated alkyl, cycloalkyl, alkenyl, aryl, alkylaryl; R' and R" areindependently H, C₁₋₄ alkyl, aryl; and L is a leaving group selectedfrom the group consisting of: ##STR49## wherein Y and Z are individuallyH, SO₃ M, CO₂ M, SO₄ M, OH, halo substituent, OR¹, R², NR³ ₃ X, andmixtures thereof, wherein M is an alkali metal or alkaline earth metalcounterion, R¹ of OR¹ is C₁₋₂₀ alkyl, R² is C₁₋₆ alkyl, R³ of NR³ ₃ isC₁₋₃₀ alkyl and X is a counterpart ion thereto, and Y and Z can be thesame or different;(ii) halide; (iii) -ONR⁴, wherein R⁴ contains at leastone carbon which is singly or doubly bonded directly to N; (iv)##STR50## wherein R⁵ is a C₁₋₁₀ alkyl; and (v) mixtures thereof; and (b)an organic binding material; wherein said granules are approximatelycylindrical or spherical, and have a diameter of about 25 to 2,000microns, and dissolve, in water, within about 10 minutes at 21° C. 19.The bleach activator granules of claim 18 wherein said binder of (b) isan organic material.
 20. The bleach activator granules of claim 19wherein said organic material is selected from the group consisting ofanionic surfactants, nonionic surfactants, water soluble organicpolymers, water dispersible organic polymers, and mixtures thereof.